Olefin metathesis has emerged as a unique and powerful transformation for the interconversion of olefinic hydrocarbons, namely due to the development of well-defined catalysts. See Grubbs, R. H. Handbook of Metathesis, Wiley-VCH: Weinheim, Germany (2003). The exceptionally wide scope of substrates and functional group tolerances makes olefin metathesis a valuable technique that quickly and efficiently produces otherwise hard to make molecules, compared to traditional synthetic organic techniques. In particular, certain Ruthenium and Osmium metal carbene compounds known as “Grubbs catalysts,” have been identified as effective catalysts for olefin metathesis reactions, such as, cross metathesis (CM), ring-closing metathesis (RCM), ring-opening metathesis (ROM), ring-opening cross metathesis (ROCM), ring-opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) polymerization. The use of such Ruthenium carbene complexes has greatly expanded the scope of olefin metathesis due to increased tolerance of organic functionality, moisture, and oxygen.
Polyamide 11 (PA11) or Nylon 11 and Polyamide 12 (PA12) or Nylon 12 are of commercial importance. Arkema sells PA11 and PA12 under the trade name of Rilsan® PA11 and Rilsan® PA12 respectively, while Evonik sells PA12 under the trade name VESTAMID® L. These high-performance polyamides possess a desirable combination of thermal, physical, chemical, and mechanical properties for industrial products, such as electrical cables, and automotive pneumatic and hydraulic hoses.
PA11 is produced from 10-undecenoic acid, derived from castor beans, and is one of the few commercially available polymers derived from a renewable resource. The limited supply of castor oil restricts the amount of PA11 produced.
PA12, which is used as a coating on fuel and braking systems on most passenger cars worldwide, is derived from cyclododecatriene (CDT).
U.S. Pat. No. 8,748,651 teaches the synthesis of long chain amino acids or esters from natural unsaturated fatty acids.
U.S. Pat. No. 8,748,651 describes the use of high catalyst loadings of olefin metathesis catalysts in the cross metathesis with acrylate.
International Patent Application Publication No. WO 2008/145941 teaches the conjugated process for the production of nitriles and/or fatty amines and of polyol carbonates by the reaction of urea with a polyol to liberate ammonia.
International Patent Application Publication No. WO 2014/122412 teaches the synthesis of amino acids from the cross metathesis of unsaturated fatty acids and esters with acrylonitrile or the cross metathesis of 9-decenenitrile and acrylates.
U.S. Patent Application Publication No. US 2014/0187808 teaches the synthesis of amino acids starting from the cross metathesis of 9-decenenitrile and acrylates.
U.S. Patent Application Publication No. US 2014/0323684 describes a method for synthesizing a ω-amino acid compound having formula HOOC—Rb—CH2NH2.
X. Miao; C. Fischmeister; P. H. Dixneuf; C. Bruneau; J.-L. Dubois; J.-L. Couturier Green Chem. (2012), 14, 2179 describes the synthesis of 12-amino acid by the cross metathesis of methyl 10-undecenoate and acrylonitrile, followed by hydrogenation to yield 12-amino acid.
R. Malacea; C. Fischmeister; C. Bruneau; J.-L. Dubois; J.-L. Couturier; P. H. Dixneuf Green Chem. (2009), 11, 152 describes the cross metathesis of acrylonitrile or fumaronitrile and unsaturated acid or ester, followed by hydrogenation to yield amino acids.
C. Bruneau; C. Fischmeister; X. Miao; R. Malacea; P. H. Dixneuf; Eur. J Lipid Sci. Technol. (2010), 112, 3-9 is a review article, which describes methyl 10-undecenoate and octadec-9-enoic diester cross metathesized with acrylonitrile or fumaronitrile to produce the unsaturated ester nitrile of the formula NCCH═CH(CH2)tCO2R.
X. Miao; R. Malacea; C. Fischmeister; C. Bruneau; P. H. Dixneuf; Green Chem. (2011), 13, 2911 teaches the slow addition of metathesis catalyst to methyl 10-undecenoate or octadec-9-enoic diester with acrylonitrile or fumaronitrile to produce the unsaturated ester nitrile of the formula NCCH═CH(CH2)dCO2R.
X. Miao; A. Blokhin; A. Pasynskii; S. Nefedov; S. N. Osipov; T. Roisnel; C. Bruneau; P. H. Dixneuf in Organometallics (2010), 29, 5257 teaches the synthesis of unsaturated ester nitrile of the formula NCCH═CH(CH2)nCO2R.
Many literature processes have been reported to produce amino acids or amino acid derivatives but all of these use high metathesis catalysts loadings to obtain sufficient yields or use toxic reagents with their metathesis catalyst. Therefore there is a need for an environmentally friendly process to produce amino acids or amino acid derivatives without high catalyst loadings or the use of toxic reagents. This invention addresses this need.